CN101772591A - Method of manufacturing a dye sensitized solar cell by atmospheric pressure atomic layer deposition (ald) - Google Patents

Method of manufacturing a dye sensitized solar cell by atmospheric pressure atomic layer deposition (ald) Download PDF

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Publication number
CN101772591A
CN101772591A CN200880101734A CN200880101734A CN101772591A CN 101772591 A CN101772591 A CN 101772591A CN 200880101734 A CN200880101734 A CN 200880101734A CN 200880101734 A CN200880101734 A CN 200880101734A CN 101772591 A CN101772591 A CN 101772591A
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layer
ald
reduce
electrolytic reaction
electric transmission
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J·费森
J·巴克
N·达特内尔
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Eastman Kodak Co
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Eastman Kodak Co
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
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  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
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  • Hybrid Cells (AREA)
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Abstract

A method of laying down one or more layers of material to reduce electrolytic reaction whilst allowing electron transfer between a conductive substrate and a light collecting charge separating layer, the layer being deposited between the conductive substrate and the light collecting charge separating layer and/or over the light collecting charge separating layer, the layer being deposited by atmospheric pressure atomic layer deposition.

Description

Make the method for dye sensitization solar battery by atmospheric pressure atomic layer deposition (ald)
Technical field
The present invention relates to solar cell, particularly relate to and be called as dye-sensitized cell and minimizing/prevent those types of undesirable reversed reaction.
Background technology
Conventional dye sensitization solar battery as by as described in the Gratzel, comprises the electrically conducting transparent base material, and for example the ITO on glass or the plastics is the titania nanoparticles sintered layer (anode) that is coated with dyestuff on it.Usually comprising iodide/triiodide carries on the hole and surface that ionogen is positioned at this layer as the hole of electronics (or hole) agent delivery.By the catalysis conductive electrode of making as catalyzer through platinum commonly used (negative electrode) is set, finish solar cell sandwich structure on ionogen.When illumination was mapped on the battery, dyestuff was excited, and electronics is injected in the titanium dioxide structure.The present positively charged dyestuff that excites is oxidizing to its oxidised form with the reduction form of the redox couple in the ionogen, and for example iodide become triiodide.It can spread to platinum electrode.When battery was connected to load, electronics arrived negative electrode from anode through load, was reduced at the oxidised form of negative electrode place redox couple, and for example triiodide becomes iodide, finishes reaction.When ionogen contacts with ITO or titanium dioxide surface, the oxidised form of redox couple also can with the electron reaction at anode place, this is called as ' reversed reaction '.If this reaction takes place, cell voltage potential and electric current are with weakened.Can select the anode conducting material to reduce this ' reversed reaction ' carefully, can not solve the problem that battery efficiency reduces fully but do like this.
It is known using composite barrier in dye sensitization solar battery, and it is mainly as the layer between titanium dioxide and the dyestuff, and conduct is arranged on the layer between active titanic dioxide mesoporosity layer and the base material electrode.Back one situation produces bottom by utilizing sputter, spraying-pyrolysis, precursor hydrolysis, microwave chemical to bathe deposition, plating or dip-coating, is resolved by other method.These method inconveniences, because they relate to solution chemistry or vacuum operating, and not necessarily consistent with existing surface shape.
US 2005/0098205 openly forms titanium dioxide bottom (in optoelectronic equipment), the undesirable contact between the material that prevents the filling template structure and the base material/base stage.This layer uses ald (ALD) formation, is the normal atmosphere step but disclose it, therefore has the equipment cost height, adds the shortcoming of time increase and vacuum type method inconvenience.
US 2005/0098204 is disclosed between first and second or second and the 3rd charge transport material, but adjacent base material forms and reduces composite inorganic layer, for example aluminum oxide.The same use of this layer ALD forms, and is the same with previous examples, do not disclose it and is the normal atmosphere step, therefore has the shortcoming that the equipment cost height adds time increase and vacuum type method inconvenience.
US 2006/0162769 open solution-type alternative method is used and the similar chemical process of ALD, i.e. metal alkoxide hydrolysis forms the coating of shape unanimity.This method is used for around the mesoporosity titanium dioxide of alumina coated in dye sensitization solar battery for example.This method has the inconvenience of solution chemistry, for example solvent and formulations prepared from solutions, and the increase of the step in the method, for example aftertreatment drying step/time.
The problem to be solved in the present invention
The purpose of this invention is to provide a kind of method, wherein " reversed reaction " of undesirable redox couple is reduced or stops fully.
By using the normal atmosphere ald, AP-ALD has been found that a kind of proper method that deposits composite barrier, and this layer is consistent with existing surface shape, and can be applied to roller to the roller manufacturing process.This layer can deposit on the anodic conductive base before laying light collection charge separating, and/or can as one man deposit on the light collection charge separating in shape before or after the staining procedure.The example that light is collected charge separating is mesoporosity titanium dioxide, zinc oxide, stannic oxide.
Summary of the invention
The present invention is for to be applied to material thin-layer on the conductive electrode (being composite barrier) of battery by AP-ALD, make electronics still can not conduct to electrode with almost having resistance, but reduce or stoped redox couple in the undesirable reversed reaction in electrode/electrolyte interface place.This layer can be reacted and sedimentary titanium dioxide on electrode surface by titanium tetrachloride and water for deriving from AP-ALD equipment.Optional layer can be oxide compound, can comprise aluminum oxide, Niobium Pentxoxide or zinc oxide.
According to the present invention, provide a kind of and lay one or more material layers to reduce the method that electrolytic reaction allows electric transmission between conductive base and the light collection charge separating simultaneously, this is deposited upon conductive base and light is collected between the charge separating and/or light is collected on the charge separating, by guiding a series of air-flows simultaneously along elongate passage, make air-flow be basically parallel to substrate surface and parallel to each other substantially, air-flow is avoided direction at adjacent elongated shape passage to flow substantially and is deposited this layer thus, wherein a series of air-flows comprise at least the first kind of reactive gaseous material in turn, inert purge gas, with second kind of reactive gaseous material, the optional repetition repeatedly, wherein first kind of reactive gaseous material can react with the substrate surface of handling with second kind of reactive gaseous material.
Beneficial effect of the present invention
By using AP-ALD as deposition method, thin composite barrier can be deposited on the anode base material and/or shape as one man is deposited on light and collects on the charge separating before or after the staining procedure, there are not cost, the shortcoming of time increase and the inconvenience of vacuum type method, or the solvent relevant and formulations prepared from solutions and step increase with solution methods, for example inconvenience of aftertreatment staining procedure/time.
Description of drawings
The present invention now will be by being described with reference to the accompanying drawings, wherein:
Fig. 1 is for describing the schema of the method steps that uses among the present invention;
Fig. 2 is the cross sectional side view of embodiment of the distributing manifold of the ald that can be used for present method;
Fig. 3 is dispensed to the cross sectional side view of the embodiment of the base material that experiences thin film deposition for gaseous material;
Fig. 4 A and 4B are the cross section view that schematically shows the embodiment of the distribution gaseous material of following deposition work;
Fig. 5 is explanation 10nm AP-ALD depositing Ti O 2Composite barrier is to the curve of Effect on Performance under 0.1 daylight, and wherein this layer directly is deposited on the ITO surface;
Fig. 6 is explanation AP-ALD depositing Ti O 2The compound block layer thickness is to the curve of the influence of dark current, and wherein these layers directly are deposited on the ITO surface;
Fig. 7 is deposited on nanoporous TiO for explanation 23nm AP-ALD ZnO composite barrier on the layer is to the curve of Effect on Performance under 0.1 daylight;
Fig. 8 is for illustrating that combined deposition is at the lip-deep 3nm AP-ALD of ITO TiO 2Composite barrier and be deposited on nanoporous TiO 2ZnO composite barrier on the layer is to the curve of Effect on Performance under 0.1 daylight; With
Fig. 9 is the curve of explanation AP-ALD composite barrier to the influence of dark current.
Detailed Description Of The Invention
Fig. 1 is a summary step diagram of putting into practice method of the present invention.Use two kinds of reactant gases, first kind of molecular precursor and second kind of molecular precursor.Gas is supplied with by source of the gas and can be supplied to base material, for example via distributing manifold.Can use and be used to supply with metering and the valve arrangement of gaseous material to distributing manifold.
Shown in step 1, supply with gaseous material continuously to system and be used for material film is deposited to base material.The step of continuous enforcement order 15.In the step 2, with respect to the given area (being called passage area) of base material, the passage area that guides first kind of molecular precursor or the relative base material of reactive gaseous material in first passage transverse flow and with the passage area reaction of base material.In the step 3, relative movement takes place in the hyperchannel stream in base material and the system, is set at step 4, and second passage (purging) stream that wherein has rare gas element takes place in given passage area.Then, in step 5, the step of step 6 is set in the relative movement of base material and hyperchannel stream, wherein given passage area is carried out ald, wherein second kind of molecular precursor given passage area transverse flow (being basically parallel to substrate surface) of base material and produce the individual layer of (in theory) material requested with aforementioned layers reaction on the base material relatively now.First kind of molecular precursor often is gas form in this method containing metal compound (for example metallic compound, for example titanium tetrachloride) and sedimentary material are containing metal compound (for example titanium dioxide).In this embodiment, second kind of molecular precursor can be for example non-metal oxidant or hydrolysis compound, for example water.
In the step 7, the step of step 8 is set in the relative movement of base material and hyperchannel stream then, wherein reuses rare gas element, and this is used for purging the excessive second kind of molecular precursor from the given passage area of abovementioned steps 6.In the step 9, relative movement takes place in base material and hyperchannel once more, sets the step of the repetitive sequence that is back to step 2.This circulation repeats repeatedly as required, to produce required film or layer.Each step can be for repeating with the given passage area of the regional corresponding base material that is covered by flow passage.Simultaneously, each passage is supplied with the gaseous material of the necessity in the step 1.With the order of square frame 15 among Fig. 1 simultaneously, other adjacency channel zone is handled simultaneously, and produces parallel hyperchannel and flows, as indicated in the whole step 11.
The main purpose of second kind of molecular precursor is that the conditioning substrate surface makes it to be reactive with first kind of molecular precursor again.Second kind of molecular precursor also provides the material of molecular gas form and one or more metallic compound combinations of surface, with the formation of containing metal precursor compound, for example oxide compound, nitride, the sulfide etc. of recent deposit.
Molecular precursor is applied to after the base material, and ALD purges and does not need to use vacuum to purge to remove molecular precursor continuously.
Suppose and use two kinds of reactant gas AX and BY that when supply response gas AX stream and given relatively substrate regions flowed, the atomic chemistry of reactant gases AX was adsorbed onto on the base material, produces the layer of A and the surface (association chemisorption) (step 2) of X ligand.Then, remaining reactant gases AX inert gas purge (step 4).Then, reactant gases BY flows, and between AX (surface) and BY (gas) chemical reaction takes place, and produces AB molecular layer (dissociative chemisorption) (step 6) on base material.Purge the by product (step 8) of remaining gas BY and reaction.The thickness of film can increase by re-treatment cycle (step 2-9).
Because film can primary depositing one deck, thus its tend to be the shape unanimity and have a uniform thickness.
With reference now to Fig. 2,, show the side cross-sectional view of an embodiment of distributing manifold 10, this distributing manifold 10 can be used for carrying out ald in the method on base material 20.Distributing manifold 10 has the inlet mouth 14 that receives first kind of gaseous material, receives the inlet mouth 16 of second kind of gaseous material and receives the inlet mouth 18 of the third gaseous material.These gases via output channel 12 discharges with following structural arrangement to output surface 36.Arrow among Fig. 2 is represented the diffusion transport by the gaseous material of output channel reception, rather than stream.Stream is drawn the accompanying drawing page in fact.
Inlet mouth 14 and 16 is suitable for receiving subsequently on substrate surface reaction and carries out ALD sedimentary first kind and second kind of gas, and inlet mouth 18 receptions are to first kind and second kind of gas inert sweeping gas.Distributing manifold 10 and base material 20 D spaced apart that on substrate carrier, provide.By moving substrate 20,, or, can between base material 20 and distributing manifold 10, provide to-and-fro movement by moving substrate 20 and distributing manifold 10 by mobile distributing manifold 10.In the particular embodiment shown in Fig. 2, base material 20 moves across output surface 36 in complex way, shown in the dotted outline of the right and left of arrow R among Fig. 2 and base material 20.Should understand for the thin film deposition of using distributing manifold 10, to-and-fro movement is always not necessary.Also can provide other relative movement type between base material 20 and distributing manifold 10, for example base material 20 or distributing manifold 10 move in one or more directions.
The sectional view of Fig. 3 is presented at the air-flow of positive 36 discharges of a part of distributing manifold 10.In this special construction, inlet mouth of seeing among each output channel 12 and Fig. 2 14,16 or one of 18 airflow connections.Each output channel 12 is supplied with first kind of reactant gaseous material O usually, or second kind of reactant gaseous material M, or the third inertia gaseous material I.
Fig. 3 shows the basis or simple layout of gas.Possible is can supply with multiple nonmetal precursors to deposit (for example material O) or multiple containing metal precursor material (for example material M) continuously in each aperture in the single deposition of film.Alternatively, when making complicated thin-film material, when for example having the alternative metal level or having the thin-film material of the doping agent of mixed with little amount in metal oxide materials, can apply the mixture of reactant gas at single output channel place, for example the mixture of the mixture of metal precursor material or metal and nonmetal precursor.Crucial requirement is to be labeled as the inertia stream of I should separate wherein any reactant channel of gas possibility interreaction.The ALD deposition is carried out in first kind and second kind of reactant gaseous material O and M interreaction, but reactant gaseous material O and M do not react with inertia gaseous material I.
The sectional view of Fig. 4 A and 4B shows below the ALD coating operation of carrying out with the schematic diagram form: when supply response thing gaseous material O and M, base material 20 is along output surface 36 processes of distributing manifold 10.Among Fig. 4 A, the surface of base material 20 at first receives from the oxygenant of being appointed as the output channel 12 of supplying with first kind of reactant gaseous material O.The surface of base material comprise now to the form of the partial reaction of the responsive material O of material M reaction.Then,, react some other thin-film material that forms metal oxide or can form by two kinds of reactant gaseous materials with M along with the path of base material 20 through the metallic compound of second kind of reactant gaseous material M.
Shown in Fig. 4 A and 4B, between first kind and second kind of reactant gaseous material O and M stream, provide inertia gaseous material I every an output channel 12.Successive output channel 12 is adjacent, also promptly share one by shown in the public border that forms of partition 22 in the embodiment.Here, output channel 12 is defined by the partition 22 that extends vertically up to base material 20 surfaces each other and separates.
It should be noted that and not introduce vacuum tunnel between the output channel 12 that promptly supplying with does not have vacuum tunnel to extract gaseous material around cutting off out yet on the passage both sides of gaseous material.By means of using air-flow of the present invention, this favourable compact Layout is possible.The gas delivery array that is different from early stage method, the early stage relative base material of method applies vertical substantially (also promptly orthogonal) air-flow, and extract waste gas out with opposite vertical direction then, distributing manifold 10 is for each reactant and rare gas element directing air flow (being preferably base layer stream in one embodiment) surfacewise, and handles waste gas and byproduct of reaction in a different manner.The air-flow that uses among the present invention along the plane of substrate surface and the plane that is parallel to surface substrate usually introduce.In other words, gas stream traverses substrate plane substantially, rather than perpendicular to the base material of handling.
Use aforesaid method and equipment to lay a blocking layer among the present invention.
Embodiment
Embodiment 1-uses and is deposited on the lip-deep TiO of ITO 2Composite barrier improves V Oc(open circuit voltage) and I Sc(short-circuit current):
Adopt the sample of 50 Ω/square ITO-PET, use AP-ALD on the ITO layer, to deposit 10nm TiO 2Composite barrier.Be used for sedimentary condition shown in the table 1.
Table 1: be used to deposit 10nm TiO 2The AP-ALD condition of composite barrier
Figure GPA00001014028500071
This carrier is used to make dye sensitization solar battery (battery A) then.Thing uses untreated 50 Ω/square ITO-PET sheet to make another dye sensitization solar battery (contrast) in contrast.
Certain titanium dioxide before using in 90 ℃ of baking ovens a dry night.This be a kind of mean particle size be 21nm the titanium dioxide sample (Degussa Aeroxide P25, specific surface area (BET)=50+/-15m 2/ g).The dye sensitization solar battery of the flexibility that following manufacturing is relevant with contrast (contrast) with the present invention (battery A).
For each sample with following quantity with exsiccant TiO 2Be dispersed in the mixture of exsiccant methyl ethyl ketone and ethyl acetate, scribbling 10nm AP-ALD TiO 2The thick nanoporous TiO of the about 15-20 μ m of deposition on the 50 Ω/square ITO-PET sample of layer and the untreated 50 Ω/square ITO-PET sample 2Film:
Degussa P25 TiO 2(21nm particle) 1.35g
Methyl ethyl ketone 45g
Ethyl acetate 5g
The SATAminijet 3 HVLP spray guns that have 1mm nozzle and 2 crust nitrogen carrier in use, spray to two conductive plastics base material samples from the distance of about 25cm before, with gained mixture sonic treatment 15 minutes.Make each layer in 90 ℃ of baking ovens dry one hour, be placed between two Teflon sheet materials, be clipped between the stainless steel cushion block of two polishings and with 3.75 tons/cm 2Pressure extrusion 15 seconds.Make sintered layer 90 ℃ of drying another hours then.
Then by sintered layer is put into cis-two-isothiocyanic acid two (2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium 3 * 10 -4Mol dm -3At a night in the ethanolic soln, make its sensitization.
The stainless steel foil electrode that under vacuum, prepares the platinum coating with sputtering sedimentation.
The TiO of dye sensitization 2Layer and platinum counter electrode are arranged with the sandwich type structure, have the ionic liquid electrolyte that is included in the liner.This ionogen comprises:
0.1M?LiI
0.6M DMPII (1,2-dimethyl-3-propyl group-imidazoles iodide)
0.05M?I 2
0.5M N-tolimidazole
Solvent=MPN (methoxypropionitrile)
After the manufacturing, by dye sensitization solar battery is placed under the light source, it is characterized, described light source is the artificial solar spectrum that reappears in the visible region, and the illuminating value of 0.10 daylight is provided.
Data presentation battery A among Fig. 5 (the present invention includes 10nm AP-ALD TiO 2Composite barrier) has open circuit voltage (Voc) and the short-circuit current (Isc) higher than the contrast that does not wherein use composite barrier.
Embodiment 2-is deposited on the lip-deep AP-ALD TiO of ITO 2The thickness of composite barrier is to the influence of dark current:
A kind of method of evaluating combined blocking layer validity is for measuring dark current.
Adopt the sample of 13 Ω/square ITO-PEN, use AP-ALD on the ITO layer, to deposit the TiO of all thickness 2Composite barrier.Be used for sedimentary condition shown in the table 2.
Table 2: the TiO that is used to deposit all thickness of battery B, C and D 2The AP-ALD condition of composite barrier
Bubbler 1 Material Water
Flow velocity ??22ml/min
Bubbler 2 Material ??TiCl 4
Flow velocity ??48ml/min
Carrier gas stream Inertia (N 2) ??2000ml/min
Water (pressurized air) ??300ml/min
Metal (N 2) ??200ml/min
Temperature Pressing plate ??95-105℃
Dispense tip ??50℃
Bubbler 1 Material Water
Deposition is provided with Pressing plate speed 25mm/ second
Head height ??55μm
Battery B Number of oscillations ??10
??TiO 2Layer thickness ??～3nm
Battery C Number of oscillations ??25
??TiO 2Layer thickness ??～6nm
Battery D Number of oscillations ??50
??TiO 2Layer thickness ??～18nm
Use the same procedure described in the embodiment 1 to make dye sensitization solar battery then.Use identical contrast (promptly do not have composite barrier, but have 13 Ω/square ITO-PEN) in this embodiment as anode base material from embodiment 1.
Measure battery B (2nm AP-ALD TiO then 2Composite barrier), C (6nm AP-ALDTiO 2Composite barrier), D (14nm AP-ALD TiO 2Composite barrier) and the contrast battery (do not have AP-ALD TiO 2Composite barrier) dark current is also shown in Figure 6.
Fig. 6 shows along with AP-ALD TiO 2The thickness of composite barrier is elevated to 18nm from zero, because compound reversed reaction, electric current is higher with voltage required before the reversed flow.
Embodiment 3-uses shape as one man to be deposited on nanoporous TiO 2ZnO composite barrier on the laminar surface, improve Voc (open circuit voltage):
Certain titanium dioxide before using in 90 ℃ of baking ovens a dry night.This be a kind of mean particle size be 21nm the titanium dioxide sample (Degussa Aeroxide P25, specific surface area (BET)=50+/-15m 2/ g).The dye sensitization solar battery of the flexibility that following manufacturing is relevant with contrast (contrast) with the present invention (battery E).
By for each sample with following quantity with exsiccant TiO 2Be dispersed in the mixture of exsiccant methyl ethyl ketone and ethyl acetate the thick nanoporous TiO of the about 30 μ m of deposition on the 13 Ω/square ITO-PEN sheet of two separations 2Film:
Degussa P25 TiO 2(21nm particle) 1.35g
Methyl ethyl ketone 45g
Ethyl acetate 5g
The SATAminijet 3HVLP spray gun that has 1mm nozzle and 2 crust nitrogen carrier in use, spray to two conductive plastics base material samples from the distance of about 25cm before, with gained mixture sonic treatment 15 minutes.Make each layer in 90 ℃ of baking ovens dry one hour, be placed between two Teflon sheet materials, be clipped between the stainless steel cushion block of two polishings and with 3.75 tons/cm 2Pressure extrusion 15 seconds.Make sintered layer 90 ℃ of drying another hours then.
For the battery relevant, use AP-ALD then at nanoporous TiO with the present invention 2Shape as one man deposits 3nm ZnO composite barrier on the surface of layer.Be used for sedimentary condition shown in the table 3.
Table 3: the AP-ALD condition that is used to deposit 3nm ZnO composite barrier
The battery relevant with contrast (contrast) is not deposited on nanoporous TiO 2ZnO layer on the laminar surface.
Then by sample is put into cis-two-isothiocyanic acid two (2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium 3 * 10 -4Mol dm -3At a night in the ethanolic soln, make its sensitization.
The stainless steel foil electrode that under vacuum, prepares the platinum coating with sputtering sedimentation.
The TiO of dye sensitization 2Layer and platinum counter electrode are arranged with the sandwich type structure, have ionic liquid electrolyte therebetween.This ionogen comprises:
0.1M?LiI
0.6M DMPII (1,2-dimethyl-3-propyl group-imidazoles iodide)
0.05M?I 2
0.5M N-tolimidazole
Solvent=MPN (methoxypropionitrile)
After the manufacturing, by dye sensitization solar battery is placed under the light source, it is characterized, described light source is the artificial solar spectrum that reappears in the visible region, and the illuminating value of 0.10 daylight is provided.
Data presentation battery E among Fig. 7 (the present invention includes and is deposited on nanoporous TiO 23nm AP-ALD ZnO composite barrier on the laminar surface) has the open circuit voltage (Voc) higher than the contrast that does not wherein use composite barrier.
Embodiment 4-uses the TiO that is deposited on the ITO base material 2Composite barrier and shape as one man are deposited on nanoporous TiO 2ZnO composite barrier on the layer, improve Voc (open circuit voltage):
Adopt the sample of 13 Ω/square ITO-PEN, use AP-ALD on the ITO layer, to deposit 3nmTiO 2Composite barrier.Be used for sedimentary condition shown in the table 4.
Table 4: be used to deposit 3nm TiO 2The AP-ALD condition of composite barrier
Figure GPA00001014028500121
This carrier is used to make dye sensitization solar battery (battery F) then.Thing uses untreated 13 Ω/square ITO-PEN sheet to make another dye sensitization solar battery (contrast) in contrast.
Certain titanium dioxide before using in 90 ℃ of baking ovens a dry night.This be a kind of mean particle size be 21nm the titanium dioxide sample (Degussa Aeroxide P25, specific surface area (BET)=50+/-15m 2/ g).The dye sensitization solar battery of the flexibility that following manufacturing is relevant with contrast (contrast) with the present invention (battery F).
By for each sample with following quantity with exsiccant TiO 2Be dispersed in the mixture of exsiccant methyl ethyl ketone and ethyl acetate the thick nanoporous TiO of the about 30 μ m of deposition on the 13 Ω/square ITO-PEN sheet of two separations 2Film:
Degussa P25 TiO 2(21nm particle) 1.35g
Methyl ethyl ketone 45g
Ethyl acetate 5g
The SATAminijet 3 HVLP spray guns that have 1mm nozzle and 2 crust nitrogen carrier in use, spray to two conductive plastics base material samples from the distance of about 25cm before, with gained mixture sonic treatment 15 minutes.Make each layer in 90 ℃ of baking ovens dry one hour, be placed between two Teflon sheet materials, be clipped between the stainless steel cushion block of two polishings and with 3.75 tons/cm 2Pressure extrusion 15 seconds.Make sintered layer 90 ℃ of drying another hours then.
For with the relevant battery of the present invention (battery F), use AP-ALD at nanoporous TiO then 2Shape as one man deposits 3nm ZnO composite barrier on the surface of layer.Be used for sedimentary condition shown in the table 5.
Table 5: the AP-ALD condition that is used to deposit 3nm ZnO composite barrier
Figure GPA00001014028500131
Figure GPA00001014028500141
Then by sample is put into cis-two-isothiocyanic acid two (2,2 '-dipyridyl-4,4 '-dicarboxylic acid) ruthenium 3 * 10 -4Mol dm -3At a night in the ethanolic soln, make its sensitization.
The stainless steel foil electrode that under vacuum, prepares the platinum coating with sputtering sedimentation.
The TiO of dye sensitization 2Layer and platinum counter electrode are arranged with the sandwich type structure, have ionic liquid electrolyte therebetween.This ionogen comprises:
0.1M?LiI
0.6M DMPII (1,2-dimethyl-3-propyl group-imidazoles iodide)
0.05M?I 2
0.5M N-tolimidazole
Solvent=MPN (methoxypropionitrile)
After the manufacturing, by dye sensitization solar battery is placed under the light source, it is characterized, described light source is the artificial solar spectrum that reappears in the visible region, and the illuminating value of 0.10 daylight is provided.
Data presentation battery F among Fig. 8 (the present invention includes and is deposited on the lip-deep 3nmAP-ALD TiO of ITO 2Composite barrier and be deposited on nanoporous TiO 23nmAP-ALD ZnO composite barrier on the laminar surface) has than the remarkable higher open circuit voltage (Voc) of the contrast that does not wherein use composite barrier.
Embodiment 5-AP-APLD composite barrier is to the influence of dark current:
For estimating the validity of each composite barrier, to battery B (the lip-deep TiO of ITO 2The blocking layer), battery E (nanoporous TiO 2On the surface sedimentary ZnO blocking layer), battery F (the lip-deep TiO of ITO 2Blocking layer and nanoporous TiO 2On the surface sedimentary ZnO blocking layer) and contrast measurement dark current (referring to Fig. 9).
Fig. 9 shows as AP-ALD TiO 2Or the ZnO composite barrier is present in ITO surface or nanoporous TiO respectively 2In the time of on the surface of layer, because the compound reversed reaction of battery when not illuminated, voltage required before the reverse direction current flow is higher.When two composite barriers of combination in a battery, required voltage even higher.This point shows that complex reaction reduces in a large number.
These embodiment show that AP-ALD can be used for depositing the composite barrier consistent with existing surface shape, and the roller that only can be applied to use the base material that is fit to machining at low temperature is to the roller manufacturing process.This one deck can be deposited on the anode base material before laying the mesoporosity titanium dioxide layer, perhaps can as one man be deposited on the mesoporosity titanium dioxide layer in shape before or after the staining procedure.
The foregoing description uses titanium dioxide to carry out.But can use any metallic compound with VI family element.
Layer thickness can be maximum 100nm.But preferred thickness is lower than 20nm, even more preferably less than 5nm.
Base material is not limited to ITO-PET.Other material be can use, membrane carrier materials, TCO coated glass are coated with such as but not limited to ITO-PEN, transparent conductive oxide (TCO).
The present invention is described in detail with reference to its preferred embodiment.It will be understood by those skilled in the art that and to carry out changes and improvements within the scope of the present invention.

Claims (10)

1. lay one or more material layers to reduce the method that electrolytic reaction allows electric transmission between conductive base and the light collection charge separating simultaneously for one kind, this is deposited upon conductive base and light is collected between the charge separating and/or light is collected on the charge separating, by guiding a series of air-flows simultaneously along elongate passage, make air-flow be basically parallel to substrate surface and parallel to each other substantially, air-flow is avoided direction at adjacent elongated shape passage to flow substantially and is deposited this layer thus, wherein a series of air-flows comprise at least the first kind of reactive gaseous material in turn, inert purge gas, with second kind of reactive gaseous material, the optional repetition repeatedly, wherein first kind of reactive gaseous material can react with the substrate surface of handling with second kind of reactive gaseous material.
2. be dye sensitization according to the process of claim 1 wherein that light is collected charge separating.
3. according to the method for claim 1 or 2, wherein reduce layer that electrolytic reaction allows electric transmission simultaneously and be metal nitride or the compound that forms by metal and VI family element.
4. according to the method for claim 3, wherein reduce electrolytic reaction and allow at least one layer of electric transmission to form simultaneously by titanium dioxide.
5. according to the method for claim 3 or 4, wherein reduce electrolytic reaction and allow at least one layer of electric transmission to form simultaneously by zinc oxide.
6. according to each method, wherein reduce each layer that electrolytic reaction allows electric transmission simultaneously and have the thickness that is lower than 100nm in preceding claim.
7. according to the method for claim 6, wherein reduce each layer that electrolytic reaction allows electric transmission simultaneously and have the thickness that is lower than 20nm.
8. according to the method for claim 7, wherein reduce each layer that electrolytic reaction allows electric transmission simultaneously and have the thickness that is lower than 5nm.
9. method of making photoelectric cell, this photoelectric cell comprise the layer of laying according to claim 1.
10. a photoelectric cell comprises the layer of making according to the method for claim 1.
CN200880101734A 2007-08-04 2008-07-02 Method of manufacturing a dye sensitized solar cell by atmospheric pressure atomic layer deposition (ald) Pending CN101772591A (en)

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